RU2742268C2 - Powders and granules and method of producing such powders and granules - Google Patents

Abstract

FIELD: chemical or physical processes.

SUBSTANCE: present invention relates to a method of producing powder or granules. Described is a method of producing powder or granules containing: (A) at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA), where said alkali metal salts are selected from compounds according to general formula (Ia) [CH₃-CH(COO)-N(CH₂-COO)₂]M_3-xH_x (Ia), where M is selected from cations of alkali metals selected from sodium, potassium or a combination of sodium and potassium, and x ranges from zero to 1.0, wherein said method includes steps of: (a) adding an aqueous solution or aqueous suspension of the corresponding chelating agent (A) to the spray granulator and removing a large portion of said water by spray granulation, using gas with inlet temperature from 125 to 250 °C, (b) extraction of granules from spray granulator, (c) separating fine particles from said granules, said fine particles having a maximum particle diameter of 350 mcm, (d) separating lumps from said granules, where said lumps have diameter of 1,000 mcm or more, (e) milling said lumps to maximum particle diameter of 500 mcm in case of granules, (f) repeated introduction of said fine particles from step (c) and crushed lumps from step (e) into a spray granulator, where fine particles share is in range from 4 to 18 wt % of total chelating agent (A) extracted in step (b), and the fraction of milled lumps from step (e) ranges from 20 to 40 wt % of the total chelating agent (A) recovered in step (b).

EFFECT: technical result is providing chelating agents in solid form, which are less hygroscopic and do not or almost do not cause yellowing when contacting percarbonate.

8 cl, 2 tbl, 5 ex

Description

The present invention relates to a method for producing a powder or granule containing

at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid ("MGDA") and glutamic acid diacetate ("GLDA") and iminodisuccinic acid ("IDS"),

wherein said method comprises the steps

(a) introducing an aqueous solution or aqueous suspension of an appropriate chelating agent (A) into a spray dryer or spray granulator, and removing most of said water by spray drying or spray granulation using a gas with an inlet temperature of 125 to 250 ° C,

(b) removing the powder or granules, respectively, from the spray dryer or spray granulator, respectively,

(c) separating fine particles from said powder or granules, wherein said fine particles have a maximum particle diameter of 30 μm in the case of powders and a maximum particle diameter of 350 μm in the case of granules, respectively,

(d) separating lumps from said powder or granules, wherein said lumps have a diameter of 250 μm or more in the case of powders and 1500 μm or more in the case of granules, respectively,

(e) grinding said lumps to a maximum particle diameter of 500 μm in the case of granules or to 40 μm in the case of powders, respectively,

(f) reintroducing said fine particles from step (c) and the comminuted lumps from step (e) into a spray dryer or spray granulator,

where the proportion of fine particles is in the range from 0.5 to 20 wt. % of the total chelating agent (A) recovered in step (b), and the proportion of crushed lumps from step (e) is in the range from 5 to 60 wt. % of the total chelating agent (A) recovered in step (b).

In addition, the present invention relates to certain powders and granules containing chelating agents.

Chelating agents of the aminocarboxylate type such as methyl glycine diacetic acid (MGDA) and glutamic diacetic acid (GLDA) and their corresponding alkali metal salts are useful sequestrants for alkaline earth metal ions such as Ca ²⁺ and Mg ²⁺ . Many aminocarboxylates show good biodegradability and are thus environmentally friendly. For this reason, they can be recommended and used for various purposes, such as laundry detergents and automatic dishwashing detergents (ADW), in particular for the so-called phosphate-free laundry detergents and phosphate-free formulations for ADW.

Depending on the type of product - liquid home care and fabric care products versus solid home care and fabric care products - and how solid home care and fabric care products are made, manufacturers may choose to process aminocarboxylate solutions or solid arminocarboxylates, for example by co-spray drying or mixing of solid particles. Powders and granules of aminocarboxylates can be transported in an economical manner due to their high content of active ingredients along with low water content. Therefore, convenient methods for preparing granules are still of great commercial interest.

WO 2009/103822 discloses a method in which slurries that have a defined solids content are granulated at an inlet gas temperature of 120 ° C or less.

WO 2012/168739 discloses a process in which suspensions of complexing agents are granulated and spray dried under non-agglomerating conditions.

Both methods have their drawbacks. Low gas inlet temperatures require highly concentrated slurries or huge amounts of gas per pellet unit. The method using non-agglomerating conditions provides only powders.

In many methods known from the prior art, it has been proposed to remove so-called fine particles, which are particles that are much smaller than the specified powder or granules, respectively, and to remove lumps, sometimes also called "excess" and grind them to the desired size. However, many methods known in the art try to avoid the formation of significant amounts of fine particles and lumps. Fine particles - and lumps - can be recycled, but the formation of a large amount obviously reduces the capacity of the drying tank.

It is desirable to provide chelating agents in solid form that are less hygroscopic and do not or almost no yellowing upon contact with the percarbonate. Therefore, it is an object of the present invention to provide chelating agents in solid form that are less hygroscopic and cause little or no yellowing on contact with percarbonate, and it is an object of the present invention to provide a method for preparing such chelating agents in solid form.

Accordingly, the method defined in the beginning was discovered, hereinafter also referred to as the method according to the present invention or as the method according to the present invention. The method according to the present invention includes several steps, which may be referred to as step (a), step (b), etc., and which are explained in more detail below.

It has been found that a relatively large amount of recycling of the crushed lumps and fines to be recycled improves the quality of the product.

The method according to the present invention is a method for producing a powder or granule. In the context of the present invention, the term "powder" refers to a particulate material that is solid at ambient temperature and which preferably has an average particle diameter in the range of 30 μm to less than 0.1 mm, preferably 30 μm to 75 μm. The average particle diameter of the powders according to the present invention can be determined, for example, by means of laser diffraction methods, for example, using a Malvern device, and refers to the average by volume.

The term "granule" in the context of the present invention refers to a particulate material that is solid at ambient temperature and which preferably has an average particle diameter (D50) in the range from 0.1 mm to 2 mm, preferably from 0.4 mm to 1.25 mm, even more preferably 400 μm to 1 mm. The average particle diameter of the granules according to the present invention can be determined, for example, by optical methods, or preferably by sieving methods. The sieves used can have a mesh in the range of 60 to 3000 microns.

In one embodiment of the present invention, the powders of the present invention or granules of the present invention have a wide particle diameter distribution. In another embodiment of the present invention, the powders of the present invention or the granules of the present invention have a narrow particle diameter distribution. The distribution of particles by diameter can be established, if necessary, through a variety of stages of sieving.

Granules and powders may contain residual moisture, with moisture referring to water, including water from crystallization and adsorbed moisture. The amount of water can be in the range from 0.1 to 20 wt. %, preferably from 1 to 15 wt. %, based on the total solids content of the respective powder or granule, and can be determined by Karl Fischer titration or by drying at 160 ° C to constant weight with infrared light.

The particles of powders and granules obtained by the method according to the present invention may have regular or irregular shapes. The preferred particle shapes of the powders obtained by the process of the present invention are spheroidal shapes.

The particles of powders and granules obtained by the method according to the present invention contain at least one chelating agent, hereinafter also referred to as chelating agent (A). The chelating agent (A) is selected from alkali metal salts of methyl glycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS).

Alkali metal salts MGDA are selected from compounds according to the general formula (Ia)

wherein

M is selected from alkali metal cations, the same or different, for example, cations of lithium, sodium, potassium, rubidium, cesium, as well as combinations of at least two of the above. Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium.

x in formula (Ia) is in the range from zero to 1.0, preferably from zero to 0.5, or from 0.1 to 0.4. In a particularly preferred embodiment of the present invention, x is zero.

The alkali metal salts GLDA are selected from compounds according to the general formula (Ib)

wherein

M is selected from alkali metal cations, the same or different as defined above,

x in formula (Ib) is in the range from zero to 2.0, preferably from zero to 0.5. In a particularly preferred embodiment of the present invention, x is zero.

Alkali metal salts IDS are selected from compounds according to the general formula (Ic)

wherein

M is selected from alkali metal cations, the same or different as defined above,

x in formula (Ic) is in the range from zero to 2.0, preferably from zero to 0.5. In a particularly preferred embodiment of the present invention, x is zero.

In one embodiment of the present invention, the alkali metal salts of MGDA are selected from lithium salts, potassium salts and preferably sodium MGDA salts. MGDA can be partially or preferably completely neutralized with a suitable alkali. In a preferred embodiment of the present invention, an average of 2.7 to 3 COOH groups of MGDA are neutralized with an alkali metal, preferably sodium. In a particularly preferred embodiment of the present invention, the chelating agent (A) is MGDA trisodium salt.

MGDA and its corresponding alkali metal salts can be selected from racemic mixtures, D-isomers and L-isomers, and from mixtures of D- and L-measurements other than racemic mixtures. Preferably, MGDA and its corresponding alkali metal salts are selected from a racemic mixture and from mixtures containing in the range from 55 to 85 mol. % Of the L-isomer, with the remainder being the D-isomer. Especially preferred are mixtures containing in the range from 60 to 80 mol. % Of the L-isomer, with the remainder being the D-isomer. Racemic mixtures are other particularly preferred embodiments of the present invention.

GLDA and its corresponding alkali metal salts can be selected from racemic mixtures, D-isomers and L-isomers, and from mixtures of D- and L-isomers other than racemic mixtures. Preferably, GLDA and its corresponding alkali metal salts are selected from a racemic mixture and from mixtures containing in the range from 55 to 99 mol. % Of the L-isomer, with the remainder being the D-isomer. Especially preferred are mixtures containing in the range from 60 to 98.5 mol. % Of the L-isomer, with the remainder being the D-isomer. Racemic mixtures are other particularly preferred embodiments of the present invention.

IDS and its corresponding alkali metal salts are selected from various mixtures of isomers, for example D, D-IDS, L, L-IDS and D, L-IDS and combinations thereof. Optically inactive mixtures are preferred because they are not expensive to manufacture.

In any case, small amounts of the chelating agent (A) may carry a cation other than the alkali metal. Thus, it is possible that small amounts, such as from 0.01 to 5 mol. % of the total MGDA, GLDA or IDS, respectively, carry an alkaline earth metal cation such as Mg ²⁺ or Ca ²⁺ , or Fe ²⁺ or Fe ³⁺ cation.

In one embodiment of the present invention, the alkali metal salt of the chelating agent (A) may contain one or more impurities that may result from the preparation of the corresponding chelating agent. In the case of MGDA and GLDA and their corresponding alkali metal salts, such impurities can be selected from propionic acid, lactic acid, alanine, nitrilotriacetic acid (NTA) or the like and their corresponding alkali metal salts. In the case of IDS, such impurities can be selected from maleic acid, maleic / fumaric acid monoamides, and racemic asparagine. Such impurities are usually present in small amounts. "Minor amounts" in this context refer to a total of 0.1 to 5 wt. %, relative to the alkali metal salt of the chelating agent (A), preferably up to 2.5 wt. %. In the context of the present invention, such small amounts are not taken into account when determining the composition of the granule obtained by the method according to the present invention.

In a particular embodiment of the present invention, a combination of alkali metal salts of at least two different chelating agents is used.

In step (a), an aqueous solution or aqueous suspension of the appropriate chelating agent (A) into a spray dryer or spray granulator.

Aqueous solutions are defined as solutions without solid particles detectable by visual inspection. In contrast, aqueous suspensions contain solid particles. The aqueous suspension contains a continuous phase and solids suspended in said continuous phase. The continuous phase of the suspension in step (a) contains water and aminocarboxylic acid (A) and is a saturated solution of aminocarboxylic acid. The continuous phase can also contain one or more inorganic salts dissolved in the continuous phase, for example, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal sulfate or an alkali metal halide, or a combination of at least two of the above.

In one embodiment of the present invention, such an aqueous solution may have a solids content in the range from 10 to 55 wt. %. The aqueous suspensions according to step (a) can have a solids content in the range from 42 to 80 wt. %. In the case of suspensions, the solids content refers to the sum of the dissolved chelating agent (A) and the sediment.

In one embodiment of the present invention, such an aqueous suspension or such aqueous solution according to step (a) has a pH in the range from 8 to 14, preferably from 9 to 13.5, and even more preferably at least 9.5. The pH is determined at ambient temperature and refers to the continuous phase.

The aqueous suspension or aqueous solution according to step (a) may have a temperature in the range from 15 to 95 ° C, preferably from 20 to 90 ° C, and even more preferably from 50 to 90 ° C.

In step (a), said aqueous suspension or said aqueous solution is introduced into an irrigation column or spray granulator. The spray granulator usually contains a fluidized bed, in the context of the present invention it is a fluidized bed of a chelating agent (A). In one embodiment of the present invention, the fluidized bed may have a temperature in the range from 80 to 150 ° C, preferably from 85 to 110 ° C.

Spraying is carried out through one or more nozzles to a spray column or spray granulator. Suitable nozzles are, for example, rotary drum high pressure atomizers, centrifugal atomizers, triple-flow nozzles, single-flow nozzles, and double-flow nozzles, with twin-flow nozzles and centrifugal atomizers being preferred. The first stream is an aqueous suspension or an aqueous solution, respectively, the second stream is a hot compressed gas, for example with a pressure of from 1.1 to 7 bar. The hot gas inlet stream may have a temperature in the range of at least 125 ° C to 250 ° C, preferably 150 to 250 ° C, even more preferably 160 to 220 ° C.

In step (a), an aqueous suspension or an aqueous solution of the complexing agent (A) is introduced in the form of drops. In one embodiment of the present invention, the droplets formed during spray granulation or spray drying have an average diameter in the range of 10 to 500 µm, preferably 20 to 180 µm, even more preferably 30 to 100 µm.

In one embodiment of the present invention, the off-gas leaving the spray tower or spray granulator, respectively, may have a temperature in the range from 40 to 140 ° C, preferably from 80 to 110 ° C, but is in any case colder than the hot gas stream. ... Preferably, the temperature of the exhaust gas leaving the drying vessel and the temperature of the solid present in the drying vessel are identical.

In one embodiment of the present invention, the pressure in the spray column or spray granulator in step (a) is ± 100 mbar normal pressure, preferably ± 20 mbar normal pressure, for example one mbar less than normal pressure.

In one embodiment of the present invention, especially in the process for producing a granule according to the present invention, the average residence time of the chelating agent (A) in step (a) is in the range from 2 minutes to 4 hours, preferably from 30 minutes to 2 hours.

In another embodiment of the present invention, spray granulation is performed by performing two or more sequential spray drying processes, for example, in a cascade of at least two spray dryers, for example, in a cascade of at least two successive spray columns or a combination of spray column and spray chamber, and the specified spray chamber contains a fluidized bed. In the first dryer, the spray drying process is performed as follows.

Spray drying may be preferred in a spray dryer such as a spray booth or spray column. An aqueous suspension or solution with a temperature preferably above ambient temperature, for example in the range from 50 to 95 ° C, is introduced into the spray dryer through one or more spray nozzles into the inlet stream of hot gas, for example nitrogen or air, when the solution or suspension is converted into drops, and the water evaporates. The incoming hot gas stream can have a temperature in the range from 125 to 350 ° C. The second spray dryer is charged with a fluidized bed of solids from the first spray dryer, and the solution or slurry obtained in the above step is sprayed onto or into the fluidized bed with the incoming hot gas stream. The incoming hot gas stream may have a temperature in the range of 125 to 350 ° C, preferably 160 to 220 ° C.

In embodiments of the present invention in which an aged suspension is used, such holding may occur in the range of 2 hours to 24 hours at a temperature preferably above ambient temperature.

During step (a), most of the water is removed. Most of the water should mean that the residual moisture content is from 0.1 to 20 wt. %, relative to powder or granule, remains. In embodiments of the present invention that start from a solution, about 51 to 75 wt. % of the water present in the aqueous solution is removed in step (a).

In step (b), the powder or granule, respectively, is removed from the spray column or spray granulator. The specified powder or granule was (was) at least partially formed during step (a) of the method according to the present invention. This removal can be accomplished through one or more openings in a spray column or spray granulator. Preferably, such one or more holes are located at the bottom of the spray column or spray granulator. Powder or granules, respectively, are removed, including fine particles and lumps.

In embodiments of the present invention, in which a powder is obtained, preferably from 70 to 95 wt. % of formed solids are recovered from the spray column per hour. In embodiments of the present invention in which a pellet is produced, 20 to 60% of the fluidized bed is recovered per hour, for example, using an extruder screw. Additional solids, especially fines, can be collected when cleaning off gas.

In step (c) of the process according to the present invention, the fine particles are separated from said powder or said granules, wherein said fine particles have a maximum particle diameter of 350 μm. Preferably, the fine particles in processes in which granules are desired may have a particle diameter in the range of 1 to 150 microns. The action of separating fine particles can be performed by sieving or air classification, preferably by sieving.

In spray drying embodiments of the present invention, the fine particles have a particle diameter of 30 microns or less, such as 1 to 30 microns.

In one embodiment of the present invention, in step (c), 40 to 100% of the fine particles present in the respective material recovered in step (b) are separated. In a preferred embodiment of the present invention, in step (c) from 80 to 99 wt. % of fine particles are separated and the remaining 1 to 20% remain in the respective powder or granule. Trying to quantitatively remove fine particles is tedious.

In step (d) of the process according to the present invention, the so-called lumps or "excess" are separated from said powder or said granules.

In embodiments of the present invention in which granules are desired, said lumps to be separated are particles that have an average particle diameter of 1000 microns, for example, from 1500 microns to 2 mm or even more. In a preferred embodiment of the present invention, the lumps are particles that have a minimum particle diameter of 1250 µm or more, even more preferably 900 µm to 2 mm.

In embodiments of the present invention in which powders are desired, said lumps or excess have a minimum particle diameter of 250 microns or more, for example, from 250 to 1000 microns.

Excess or lumps can be removed, for example with an unloading auger or a rotary valve, usually with the target product, and then classified.

It is observed that in connection with step (e), the smaller the maximum size of the lumps to be separated in step (d), the better the hygroscopic behavior of the subsequent chelating agent and the higher the peroxide stability.

Steps (c) and (d) can be performed in any order, sequentially or simultaneously.

In one embodiment of the present invention, the amount of powder or granule, respectively, other than fine particles and excess is in the range from 55 to 70 wt. %, with reference to the total amount of material removed in step (b).

). Другими примерами являются вальцовые мельницы и шаровые мельницы.In step (e) of the method according to the present invention, the lumps separated in step (d) are ground to a maximum particle diameter of 500 µm, preferably to a maximum particle diameter of 400 µm. Grinding can be carried out in any type of mill. Examples of particularly useful mills are jet mills, pin mills, and screening machines (in German:

). Other examples are roller mills and ball mills.

From step (e) a particulate material is obtained. It generally has a broad particle diameter distribution, in embodiments of the present invention in which granules are desired, such particulate material may have particles that have a particle diameter in the range of 1 to 500 microns.

In step (f) of the method according to the present invention, said fine particles from step (c) and the comminuted lumps from step (e) are reintroduced into a spray dryer or spray granulator. Such re-introduction can be carried out by pneumatic conveying of said fine particles from step (c) and comminuted lumps from step (e) into an irrigation column or spray granulator, respectively, preferably through an additional opening rather than together with the solution or suspension from step (a ).

The proportion of fine particles recovered in step (b) is in the range from 0.5 to 20 wt. % of the total chelating agent (A) recovered in step (b), preferably from 4 to 18 wt. %. The proportion of lumps is in the range from 5 to 60 wt. % of the total chelating agent (A) recovered in step (b), preferably from 20 to 40 wt. % and even more preferably from 25 to 35 wt. %. With a higher proportion of lumps, the process according to the present invention becomes economically disadvantageous because it is too much recycling. With fewer lumps, the hygroscopicity becomes too high.

In one embodiment of the present invention, the chelating agent (A) is spray dried or spray gunned, respectively, without any additive such as (co) polymer or silica or surfactant. In other embodiments of the present invention, the chelating agent (A) is spray dried or spray granulated, respectively with an additive selected from (co) polymer, hereinafter also referred to as (co) polymer (B), or with the addition of polyvinyl alcohol or silica ...

In one embodiment of the present invention, the aqueous solution or aqueous suspension from step (a) contains at least one additive selected from silica, silicates, inorganic salts, (co) polymers (B) and complexing agents other than aminocarboxylic acid ( A) and organic (co) polymers. Such additive (s) may also be referred to as additive (s) (B). This can be done by adding one or more additives (B) to the aqueous suspension or solution at any stage prior to step (b). Examples of additives (B) used are, for example, titanium dioxide, sodium carbonate, potassium carbonate, sugar, silica gel, sodium silicate, potassium silicate, and (co) polymers (B), such as, but not limited to, polyacrylates, polyalkyleneimines such as polyethyleneimines, alkoxylated polyethyleneimines, carboxymethylated polyethyleneimines, and polyvinyl alcohol. Polyvinyl alcohol in the context of the present invention refers to fully or partially hydrolyzed polyvinyl acetate. In partially hydrolyzed polyvinyl acetate, at least 95 mol. %, preferably at least 96 mol. % of the acetate groups were hydrolyzed. Examples of complexing agents other than aminocarboxylic acid (A) are alkali metal citrates. Another possible class of additives are phosphonates, for example the alkali metal salts of hydroxyethane-1,1-diphosphonic acid, "HEDP".

In one embodiment of the present invention, the polyvinyl alcohol has an average molecular weight M _w in the range of 22,500 to 115,000 g / mol, for example up to 40,000 g / mol. In one embodiment of the present invention, the polyvinyl alcohol has an average molecular weight M _n in the range of 2,000 to 40,000 g / mol.

In one embodiment of the present invention, the aqueous suspension subjected to spray granulation in step (c) contains from 0.05 to 30 wt. % additive (s) (s) in general, with percentages referring to the aqueous suspension as a whole. The amount of polyethyleneimines or alkoxylated polyethyleneimines is preferably in the range from 0.05 to 0.5 wt. %, the amount of silicate can be up to 30 wt. %.

Examples of (co) polymers (B) are poly (meth) acrylates, polyalkyleneimines, especially polyethyleneimines, and substituted polyalkyleneimines, for example polycarboxymethylated polyethyleneimines, polycarboxyethylated polyalkyleneimines, and polyalkoxylated polyethyleneimines, especially polyethoxylated polyethyleneimines.

Preferred examples of polycarboxymethoxylated polyethyleneimines are polyethyleneimines, in which from 20 to 90 mol. % Of the N-atoms carry at least one CH ₂ COO ^- group, and their corresponding alkali metal salts, especially their sodium salts.

In one embodiment of the present invention, said suspension or solution in step (a) contains in the range from 80 to 99.9 wt. % of the chelating agent (A) and from 0.1 to 20 wt. % (co) polymer (B), the percentages referring to the total solids content of said aqueous suspension or solution.

In one embodiment of the present invention, the (co) copolymers (B) selected from poly (meth) acrylic acid have an average molecular weight M _w in the range of 1200 to 30,000 g / mol, as determined by gel permeation chromatography and with reference to the appropriate free acid, if applicable.

In one embodiment of the present invention, the aqueous solution or suspension in step (a) contains at least one (co) polymer (B), said (co) polymer (B) being selected from homo- and copolymers of (meth) acrylic acid and polyalkyleneimines which may be polyalkoxylated or substituted carboxymethyl groups.

In one embodiment of the present invention, the method of the present invention may comprise one or more additional steps (g). For example, a post-drying step (g), sometimes also called thermal post-treatment, is possible after step (b) on a material that is neither fine particles nor lumps. Thermal post-treatment can be performed in an oven, for example, at a temperature in the range from 80 to 120 ° or with hot steam, at a temperature of from 100 to 160 ° C.

Powders and granules with excellent properties can be obtained by carrying out the method of the present invention. They not only show good properties in terms of biodegradability and complexation behavior, but also show low hygroscopicity and excellent behavior towards peroxides and percarbonates.

Another object of the present invention is powders and granules containing at least one chelating agent selected methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and their corresponding alkali metal salts, said powders and granules further also are referred to as powders according to the present invention and as granules according to the present invention, respectively.

The powders of the present invention and the granules of the present invention contain

(A) at least one chelating agent selected from methyl glycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and their corresponding alkali metal salts,

with a degree of crystallinity in the range from 75 to 86%, determined by means of X-ray diffraction.

The chelating agents (A) have been described in detail above.

The degree of crystallinity, in the context of the present invention, also simply called crystallinity, was determined from the X-ray powder diffractogram in a known manner, as usual, by determining the surface fraction of the crystalline phase and the amorphous phase and using them to calculate the degree of crystallinity CD, as the ratio of the area of the crystalline phase, Ic, and the total area consisting of the combined areas of the amorphous phase, Ia, and the area of the crystalline phase, Ic:

CD = I _c / (I _c + I _a ).

In particular, the determination of the degree of crystallinity can be performed using software, for example TOPAS® software from Bruker AXS.

The determination of the degree of crystallinity was carried out using an X-ray powder diffractogram in accordance with the method of relative intensities. Data are collected on a standard Bragg-Brentano diffractometer using CuKα radiation. An area from 2 ° to 50 ° (2θ) is scanned using a step size of 0.02 °. The primary and secondary programmable motorized slit is set to provide a constant illuminated sample length of 20 mm. The diffraction pattern is modeled using the Rietveld method, aligning the diffraction pattern to the experimental data. The model includes the following parameters: linear background function, Lorentz and polarization corrections, complete crystal structures of form I and form II MGDA-Na ₃ . The latter contribute to the crystal intensity (I _crystal ) for the simulated model. The _amorphous intensity (I _amorphous ) is modeled using two Lorentz functions centered at 8 ° (2θ) and 36.2 ° 2θ). Peak positions, intensities and widths were refined to match the measured data. This model was created and improved in the commercial software TOPAS V4.2 (Bruker AXS GmbH, Karlsruhe). The crystallinity K was then determined using the function:

In accordance with the above explanations, the salts of the present invention can exist as a racemic mixture (D, L) or as a pure L- or D-enantiomer, of which the L-enantiomer is preferred - or as a mixture of L- and D-enantiomers, in which one of the enantiomers is predominantly present, for example, in mixtures with an enantiomeric excess (ee) of the L-enantiomer in the range from 0.1 to 85%. Preferred are racemic mixtures and mixtures of enantiomers containing predominantly the corresponding L-isomer with an enantiomeric excess (ee) in the range of 0.1 to 85%, even more preferably 2.5 to 50%.

In one embodiment of the present invention, the powders of the present invention and the granules of the present invention have a residual moisture content in the range of 1 to 20 wt. %. The residual moisture content can be determined by Karl-Fischer titration or by drying at 160 ° C to constant weight with infrared light.

In one embodiment of the present invention, the powders of the present invention have an average diameter in the range from 30 μm to 95 μm, especially from 30 to 75 μm.

In one embodiment of the present invention, the pellet according to the present invention has an average particle diameter in the range of 0.35 mm to 1.5 mm, preferably 350 to 1000 μm, even more preferably up to 900 μm. The largest number of particles preferably has an average particle diameter in the range of 600 to 750 µm.

Another aspect of the present invention is the use of the powders of the present invention and the granules of the present invention, and another aspect of the present invention is methods of using the powders of the present invention and the granules of the present invention. A preferred use of the powders of the present invention and the granules of the present invention is to prepare solid laundry detergent compositions and solid detergent compositions for cleaning a hard surface. Solid compositions of detergents for washing and solid compositions of detergents for cleaning a hard surface may contain some residual moisture, for example, from 0.1 to 10 wt. %, but otherwise are solid mixtures. The residual moisture content can be determined, for example, under vacuum at 80 ° C. Another object of the present invention is to provide solid laundry detergent compositions and solid detergent compositions for cleaning a hard surface.

In the context of the present invention, the term "detergent composition for cleaning agents" includes cleaning agents for home care and for industrial or institutional applications. The term "detergent composition for cleaning agents for hard surfaces" includes compositions for washing dishes, especially manual dishwashing and automatic dishwashing and washing products, and compositions for cleaning hard surfaces such as, but not limited to, cleaning compositions bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, vehicle cleaning, including cleaning of trucks, in addition, for cleaning open shops, washing without disassembly, cleaning metals, disinfecting cleaning, cleaning farms, cleaning under high pressure, but not the composition of detergents for washing.

In the context of the present invention and unless otherwise indicated, the percentages in the context of the ingredients of the laundry detergent compositions are percentages by weight and refer to the total solids content of the corresponding laundry detergent composition. In the context of the present invention and unless otherwise indicated, the percentages in the context of the ingredients of the hard surface cleaning detergent composition are percentages by weight and refer to the total solids content of the hard surface cleaning detergent composition.

In one embodiment of the present invention, the solid compositions of detergents for laundry according to the present invention may contain in the range from 1 to 30 wt. % of the powder according to the present invention or the granule according to the present invention, respectively. Percentages refer to the total solids content of the respective laundry detergent composition.

In one embodiment of the present invention, the solid detergent compositions for cleaning hard surfaces according to the present invention may contain in the range from 1 to 50 wt. % of the powder according to the present invention or the granule according to the present invention, respectively, preferably from 5 to 40 wt. % and even more preferably 10 to 25 wt. %. Percentages refer to the total solids content of the corresponding detergent composition for cleaning hard surfaces.

Particularly preferred solid hard surface cleaning detergent compositions of the present invention and solid laundry detergent compositions of the present invention, especially for home care, may contain one or more complexing agents other than the salt of the present invention. The solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention may contain one or more chelating agents (also referred to as sequestrants in the context of the present invention) other than the salt of the present invention. Examples of sequestrants other than the salt of the present invention are IDS (iminodisuccinate), citrate, phosphonic acid derivatives such as hydroxy-ethane-1,1-diphosphonic acid disodium salt ("HEDP"), and polymers with complexing groups such as , polyethyleneimine, in which from 20 to 90 mol. % N-atoms carry at least one CH ₂ COO ^- group and their respective alkali metal salts, especially their sodium salts, such as GLDA-Na _4, IDS-Na _4, and trisodium citrate, and phosphates such as STPP (tripolyphosphate sodium). Because phosphates are detrimental to the environment, it is preferred that preferred detergent compositions and preferred laundry detergents are free of phosphate. The term "free of phosphate" as to be understood in the context of the present invention means that the content of phosphate and polyphosphate in total ranges from 10 ppm to 0.2 wt. % as determined by gravimetry.

Preferred solid hard surface cleaning detergent compositions of the present invention and preferred solid laundry detergent compositions of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

Preferred nonionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APGs), hydroxyalkyl mixed ethers and amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, the compounds of general formula (III)

in which the variables have the following meanings:

R ² is identical or different and is selected from hydrogen and linear C ₁ -C ₁₀ -alkyl, preferably in each case is identical and is ethyl, and particularly preferably hydrogen or methyl,

R ³ is selected from C ₈ -C ₂₂ -alkyl, branched or linear, for example n-C ₈ H ₁₇ , n-C ₁₀ H ₂₁ , n-C ₁₂ H ₂₅ , n-C ₁₄ H ₂₉ , n-C ₁₆ H ₃₃ or n-C ₁₈ H ₃₇ ,

R ⁴ is selected from C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl , 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

e and f are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range from 3 to 50. Preferably, m is in the range from 1 to 100, and n is in the range from 0 to 30 ...

In one embodiment of the present invention, the compounds of general formula (III) may be block copolymers or random copolymers, block copolymers being preferred.

Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (IV)

in which the variables are defined as follows:

R ² is identical or different and is selected from hydrogen and linear C ₁ -C ₀ -alkyl, preferably in each case is identical and is ethyl, and particularly preferably hydrogen or methyl,

R ⁵ is selected from C ₆ -C ₂₀ -alkyl, branched or linear, in particular n-C ₈ H ₁₇ , n-C ₁₀ H ₂₁ , n-C ₁₂ H ₂₅ , n-C ₁₃ H ₂₇ , n-C ₁₅ H ₃₁ , n-C ₁₄ H ₂₉ , n-C ₁₆ H ₃₃ , n-C ₁₈ H ₃₇ ,

a is a number in the range from zero to 10, preferably from 1 to 6,

b is a number in the range from 1 to 80, preferably from 4 to 20,

d is a number in the range from zero to 50, preferably from 4 to 25.

The sum of a + b + d is preferably in the range from 5 to 100, even more preferably in the range from 9 to 50.

Preferred examples of hydroxyalkyl mixed ethers are compounds of general formula (V)

in which the variables are defined as follows:

R ² is identical or different and is selected from hydrogen and linear C ₁ -C ₁₀ -alkyl, preferably in each case is identical and is ethyl, and especially preferably hydrogen or methyl,

R ³ is selected from C ₈ -C ₂₂ -alkyl, branched or linear, for example iso-C ₁₁ H ₂₃ , iso-C ₁₃ H ₂₇ , n-C ₈ H ₁₇ , n-C ₁₀ H ₂₁ , n-C ₁₂ H ₂₅ , n-C ₁₄ H ₂₉ , n-C ₁₆ H ₃₃ or n-C ₁₈ H ₃₇ ,

R ^{5 is} selected from C ₆ -C ₂₀ -alkyl, e.g. n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

The variables m and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range from 5 to 50. Preferably, m is in the range from 1 to 100, and n is in the range from 0 to thirty.

Compounds of general formula (IV) and (V) can be block copolymers or random copolymers, with block copolymers being preferred

Other suitable nonionic surfactants are selected from di- and multiblock copolymers of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amino oxides or alkyl polyglycosides, especially linear C ₄ -C ₁₆ alkyl polyglycosides and branched C ₈ -C ₁₄ alkyl polyglycosides, such as compounds of general formula (VI), are likewise suitable.

Where:

R ⁶ is C ₁ -C ₄ -alkyl, in particular ethyl, n-propyl or isopropyl,

R ⁷ represents - (CH ₂ ) ₂ -R ⁶ ,

G ¹ is selected from monosaccharides with 4-6 carbon atoms, especially from glucose and xylose,

y is in the range from 1.1 to 4, with y being the average,

Other examples of nonionic surfactants are compounds of general formula (VII) and (VII)

AO is selected from ethylene oxide, propylene oxide and butylene oxide,

EO is ethylene oxide, CH ₂ CH ₂ -O,

R ⁸ is selected from C ₈ -C ₁₈ branched or linear alkyl, and R ⁵ is as defined above.

A ³ O is selected from propylene oxide and butylene oxide,

w is a number in the range from 15 to 70, preferably from 30 to 50,

w1 and w3 are numbers between 1 and 5, and

w2 is a number between 13 and 35.

An overview of other suitable nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187.

Mixtures of two or more different nonionic surfactants selected from the above may also be present.

Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

Examples of amphoteric surfactants are those that carry a positive and a negative charge in the same molecule under the conditions of use. Preferred examples of amphoteric surfactants are so-called betaine surfactants. Many examples of betaine surfactants carry one quaternized nitrogen atom and one carboxylic acid group per molecule.

A particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).

Examples of amine oxide surfactants are compounds of general formula (IX)

where R ⁹ , R ¹⁰ , and R ^{11 are} independently selected from aliphatic, cycloaliphatic or C ₂ -C ₄ -alkylene-C ₁₀ -C ₂₀ -alkylamido moieties. Preferably, R ⁹ is selected from C ₈ -C ₂₀ alkyl or C ₂ -C ₄ alkylene-C ₁₀ -C ₂₀ alkylamido, and R ¹⁰ and R ^{11 are} both methyl.

A particularly preferred example is lauryl dimethylamine oxide, sometimes also called lauramine oxide. Another particularly preferred example is cocamidylpropyl dimethylamine oxide, sometimes also called cocamidopropylamine oxide.

Examples of suitable anionic surfactants are alkali metal salts and ammonium salts of C ₈ -C ₁₈ alkyl sulfates, polyether sulfates of C ₈ -C ₁₈ fat alcohols, half-esters of sulfuric acid and ethoxylated C ₄ -C ₁₂ alkyl phenols (ethoxylation: from 1 to 50 mol of ethylene oxide / mol), alkyl esters of C ₁₂ -C ₁₈ fatty sulfo-acids, for example methyl esters of C ₁₂ -C ₁₈ fatty sulfonic acids, in addition, C ₁₂ -C ₁₈ -alkylsulfonic acids and C ₁₀ - C ₁₈ -alkylaryl sulfonic acids. The alkali metal salts of the above compounds are preferred, especially the sodium salts.

Other examples of suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkyl ether phosphates.

Preferably, the laundry detergent compositions of the present invention contain at least one anionic surfactant.

In one embodiment of the present invention, the solid compositions of detergents for laundry according to the present invention may contain from 0.1 to 60 wt. % of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

In one embodiment of the present invention, the solid detergent compositions for cleaning agents according to the present invention may contain from 0.1 to 60 wt. % of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

In a preferred embodiment of the present invention, the solid detergent compositions for the cleaning agents of the present invention, and especially for automatic dishwashing cleaners, do not contain any anionic surfactant.

The solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention may contain at least one bleaching agent, also referred to as bleach. The whitening agents can be selected from chlorine bleach and peroxide bleach, and the peroxygen bleach can be selected from inorganic peroxide bleach and organic peroxide bleach. Preferred are inorganic peroxide brighteners selected from alkali metal percarbonate, alkali metal perborate and alkali persulfate.

Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.

In the solid hard surface cleaning detergent compositions of the present invention and in the solid laundry detergent compositions of the present invention, alkali metal percarbonates, especially sodium percarbonates, are preferably used in the form of an applied coating. Such coatings can be organic or inorganic in nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the above, for example, a combination of sodium carbonate and sodium sulfate.

Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Solid compositions of detergents for cleaning hard surfaces according to the present invention and solid compositions of detergents for laundry according to the present invention may contain, for example, in the range from 3 to 10 wt. % chlorine bleach.

The solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention may contain one or more bleaching catalysts. The bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as, for example, manganese, iron, cobalt, ruthenium, or molybdenum-selenium complexes, or carbonyl complexes. Complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleaching catalysts.

Solid detergent compositions for cleaning hard surfaces of the present invention and solid compositions of detergents for laundry according to the present invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quaternary salts (trimethylammonium acetonitrile salts).

Other examples of suitable bleach promoters are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

The solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention may contain one or more corrosion inhibitors. In this case, it should be clear how to include such compounds that inhibit metal corrosion. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles as well as phenolic derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, the solid detergent compositions for cleaning hard surfaces of the present invention and the solid compositions of detergents for washing according to the present invention contain in general in the range from 0.1 to 1.5 wt. % corrosion inhibitor.

The solid detergent compositions for cleaning hard surfaces according to the present invention and the solid detergent compositions for washing according to the present invention may contain one or more structuring agents selected from organic and inorganic structuring agents. Examples of suitable inorganic structurants are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layered silicates, in particular of the formulas α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , and δ- Na ₂ Si ₂ O ₅ , as well as fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric structure formers, for example, polycarboxylates and polyaspartic acid.

Examples of organic structuring agents are, in particular, polymers and copolymers. In one embodiment of the present invention, the organic nucleating agents are selected from polycarboxylates, for example homopolymers of alkali metal salts of (meth) acrylic acid or copolymers of (meth) acrylic acid.

Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M _w in the range from 2000 to 40,000 g / mol, preferably from 2000 to 10,000 g / mol, in particular from 3000 to 8000 g / mol. Also suitable are copolymeric polycarboxylates, in particular acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid and / or fumaric acid, and with the same molecular weight range.

It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ mono- or C ₄ -C ₁₀ dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilic or hydrophobic monomer as listed below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with 10 or more carbon atoms, or mixtures thereof, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule ...

Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, as well as non-ionic monomers with hydroxyl functional group or alkylene oxide groups. As an example, allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate) ethoxypolypolypol meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols according to the present invention may contain from 3 to 50, in particular from 5 to 40 and especially from 10 to 30 alkylene oxide units per molecule.

Particularly preferred monomers containing a sulfonic acid group according to the present invention are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3 -methacrylamido-2-hydroxypropanesulfonic acid, allyl sulfonic acid, metal sulfonic acid, allyloxybenzenesulfonic acid, metalloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid vinyl sulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide, and salts of these acids such as their sodium, potassium or ammonium salts.

Particularly preferred monomers containing a sulfonic acid group are vinyl phosphonic acid and its salts.

Another example of structurant is carboxymethylinulin.

Moreover, amphoteric polymers can also be used as structurants.

Solid compositions of detergents for cleaning hard surfaces according to the present invention and solid compositions of detergents for laundry according to the present invention may contain, for example, in general in the range from 10 to 70 wt. %, preferably up to 50 wt. %, structurant. In the context of the present invention, MGDA is not considered a structurant.

In one embodiment of the present invention, the solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention may contain one or more builders.

The solid detergent compositions for cleaning hard surfaces of the present invention and the solid detergent compositions for washing according to the present invention may contain one or more antifoam agents selected from, for example, silicone oils and paraffin oils.

In one embodiment of the present invention, the solid detergent compositions for cleaning hard surfaces of the present invention and the solid compositions of detergents for washing according to the present invention generally contain in the range from 0.05 to 0.5 wt. % antifoam agent.

Solid detergent compositions for cleaning hard surfaces of the present invention and solid compositions of detergents for washing according to the present invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterase, pectinase, lactase, and peroxidase.

In one embodiment of the present invention, solid compositions of detergents for cleaning hard surfaces according to the present invention and solid compositions of detergents for washing according to the present invention may contain, for example, up to 5 wt. % enzyme, preferably from 0.1 to 3 wt. %. Said enzyme can be stabilized, for example, with the sodium salt of at least one C ₁ -C ₃ carboxylic acid or C ₄ -C ₁₀ dicarboxylic acid. Formates, acetates, adipates and succinates are preferred.

In one embodiment of the present invention, the solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention contain at least one zinc salt. Zinc salts can be selected from water-soluble and water-insoluble zinc salts. In this regard, in the context of the present invention, the term "water-insoluble", as used, refers to those zinc salts which, in distilled water at 25 ° C., have a solubility of 0.1 g / L or less. Zinc salts which have a higher solubility in water are accordingly referred to in the context of the present invention as water-soluble zinc salts.

In one embodiment of the present invention, the zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate, preferably ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate.

In another embodiment of the present invention, the zinc salt is selected from ZnO, ZnO⋅aq, Zn (OH) ₂ and ZnCO ₃ . ZnO⋅aq is preferred.

In one embodiment of the present invention, the zinc salt is selected from zinc oxides with an average particle diameter (weight average) in the range of 10 nm to 100 μm.

The cation in the zinc salt can be present in a complex form, for example complexed with ammonia ligands or water ligands, and in particular can be present in a hydrated form. For simplicity of notation, in the context of the present invention, ligands are generally omitted when they are water ligands.

Depending on how the pH of the mixture according to the present invention is adjusted, the zinc salt may vary. Thus, for example, it is possible to use zinc acetate or ZnCl ₂ to prepare a composition according to the present invention, but this salt is converted at a pH of 8 or 9 in an aqueous environment to ZnO, Zn (OH) ₂ or ZnO⋅aq, which can be present in uncomplexed form or in the form of a complex.

The zinc salt may be present in those detergent compositions for cleaning agents according to the present invention that are solid at room temperature and preferably present in particulate form, which have, for example, a mean diameter (number average) in the range from 10 nm to 100 μm, preferably 100 nm to 5 μm, as determined, for example, by X-ray scattering.

The zinc salt can be present in those home detergent compositions that are liquid at room temperature, in dissolved form, or in solid or colloidal form.

In one embodiment of the present invention, the composition of detergents for cleaning agents and compositions of detergents for laundry generally contain in the range from 0.05 to 0.4 wt. % zinc salt, in each case based on the solids content of the composition in question.

According to the present invention, the zinc salt fraction is regarded as zinc or zinc ions. Based on this, it is possible to calculate the counterion fraction.

In one embodiment of the present invention, the solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention are free of heavy metals other than zinc compounds. In the context of the present invention, this is understood to mean that the detergent compositions and the laundry detergent compositions according to the present invention are free of those heavy metal compounds that do not act as whitening catalysts, in particular free of iron compounds and bismuth. In the context of the present invention, the expression "free of" in relation to heavy metal compounds is understood to mean that the content of heavy metal compounds that do not act as bleaching catalysts totals in the range from 0 to 100 ppm, as defined by leaching and based on solids content. Preferably, the composition of the present invention has a heavy metal content, excluding zinc, of less than 0.05 ppm, based on the solids content of the composition in question. The zinc fraction is thus not included.

In the context of the present invention, the term "heavy metals" means any metal with a specific density of at least 6 g / cm ³ , with the exception of zinc. In particular, heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium, and chromium.

Preferably, the solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention contain unmeasured fractions of bismuth compounds, i.e., for example, less than 1 ppm.

In one embodiment of the present invention, the solid hard surface cleaning detergent compositions of the present invention and the solid laundry detergent compositions of the present invention contain one or more other ingredients such as fragrances, colorants, organic solvents, buffers, disintegrants for tablets, and / or acids such as methylsulfonic acid.

Preferred exemplary automatic dishwashing detergent compositions can be selected according to Table 1.

The laundry detergent compositions of the present invention are useful for washing any type of laundry and any type of fiber. The fibers can be of natural or synthetic origin, or can be mixtures of natural and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples of fibers of synthetic origin are polyurethane fibers such as Spandex® or Lycra®, polyester fibers, or polyamide fibers. The fibers can be individual fibers or portions of fabrics such as knitted fabrics, woven fabrics or non-woven fabrics.

The present invention is further illustrated by working examples.

General remarks:

X-ray powder diffractometer measurements were performed on a D8 Advance® diffractometer from Bruker AXS (Karlsruhe). In reflection with Cu — K, α radiation was measured with an adjustable aperture adjustable on the primary side and the secondary side. The measurement range was 2 ° to 80 ° 2-theta, the step width was 0.01 °, and the measurement time per angle step was 3.6 seconds.

The hygroscopicity was determined by storage at 25 ° C and 50% relative humidity for 24 hours. Alternatively, the so-called tropical conditions were maintained at 35 ° C and 70 to 90% relative humidity for 24 hours. Rating: zero (free flowing granule / powder) to 4 (granule / powder dissolved).

With the exception of its values and degrees of crystallinity, percentages in the context of the examples refer to wt. % unless explicitly stated otherwise.

Normal pressure: 1013 mbar

Mean particle diameters (D50) were determined by sieving methods, unless otherwise indicated.

Chelating agent (A.1): MGDA-Na ₃ (65% L-MGDA-Na ₃ , 35% D-MGDA-Na ₃ ) provided as 40 wt. % aqueous solution, pH: 9.5.

Polymer (B.1): polyethyleneimine, density: 1.03 g / cm ³ , M _w : 800 g / mol, M _n : 600 g / mol

Polymer (B.2): polyacrylic acid completely neutralized with Na, K-value according to Fickentcher: 30 in 1 wt% aqueous solution at pH 7, density: 1.20 g / cm ³

Example 1

Stage (a.1): the aqueous solution (A.1) was heated to 80 ° C.

A vessel containing a fluidized bed of 1 kg of solid MGDA-Na ₃ granules, an initial average particle diameter of 550 μm, was provided. Fluidization was carried out by introducing a so-called fluidizing gas at the bottom of the vessel, said fluidizing gas being air with an inlet temperature of 150 ° C.

Once a bed temperature of at least 105 ° C. was reached, an amount of 2 kg / h of the above aqueous solution (A.1) was sprayed onto the fluidized bed using a nozzle. Sputtering - and so-called atomization - was carried out using air with an inlet gas temperature of 150 ° C.

Step (b.1): Every 30 minutes, an aliquot of the pellet was removed from the vessel through the side discharge auger.

Steps (c.1) and (d.1): The aliquot recovered in accordance with step (b.1) was classified by sieving in a twin sieve sieve, 350 µm and 1250 µm mesh. Shares 25 wt. % lumps having a minimum diameter of 1250 microns, and 7 wt. % of fine particles having a maximum diameter of 350 μm were separated.

Stage (e.1): The lumps obtained in stage (d.1) were milled in a hammer mill, type Kinematica Polymix System PM-MFC 90 D. Milled particles with a maximum diameter of 500 μm were collected and transferred to stage (f).

Step (f.1) The crushed lumps obtained in step (e.1) were combined with the fine particles from step (c.1) and returned in portions to the granulator.

A free-flowing granule (A.1) was obtained which had excellent properties such as, but not limited to, excellent percarbonate stability and low hygroscopicity. No hot spots were observed during processing. No sticky material was obtained. A free-flowing granule was obtained and the hygroscopicity was low.

Example 2

Example 1 was basically repeated with the following differences:

At stage (a.2), an aqueous solution (A.1), a concentration of 40 wt. %, and (B.1), 0.25 wt. %, heated to 80 ° C and then spray granulated.

At stage (c.2), 13 wt. % of fine particles were removed. At stage (d.2), 28 wt. % the lumps were removed.

The subsequent stages were repeated with appropriate changes.

A free-flowing co-granule (A.1) and (B.1) is obtained which has excellent properties such as, but not limited to, excellent percarbonate stability and low hygroscopicity. No hot spots were observed during processing. No sticky material was obtained. The hygroscopicity was low.

Example 3

Example 1 was basically repeated with the following differences:

At stage (a.3), an aqueous solution (A.1), a concentration of 40 wt. %, and (B.1), 10 wt. %, heated to 80 ° C and then spray granulated.

At stage (c.3), 8 wt. % fine particles were removed. At stage (d.3), 26 wt. % the lumps were removed.

The subsequent stages were repeated with appropriate changes.

A free-flowing co-granule (A.1) and (B.1) is obtained which has excellent properties such as, but not limited to, excellent percarbonate stability and low hygroscopicity. No hot spots were observed during processing. No sticky material was obtained. The hygroscopicity was low.

Example 4

Stage (a.4): the aqueous solution (A.1) was heated to 55 ° C.

A vessel containing a fluidized bed of 1 kg of solid MGDA-Na ₃ granules, an initial average particle diameter of 550 μm, was provided. Fluidization was carried out by introducing a so-called fluidizing gas at the bottom of the vessel, said fluidizing gas being air with an inlet temperature of 150 ° C.

Once a bed temperature of at least 99 ° C. was reached, an amount of 2 kg / h of the above aqueous solution (A.1) was sprayed onto the fluidized bed using a nozzle. Atomization - and so-called atomization - was carried out using air with an inlet gas temperature of 160 ° C and a pressure of 2.8 bar.

Step (b.4): Every 30 minutes, an aliquot of the pellet was removed from the vessel through the side discharge auger. The residual moisture content was 9.5 wt. %.

Steps (c.4) and (d.4): The aliquot recovered according to step (b.4) was classified by sieving in a twin sieve sieve, 350 µm and 1250 µm mesh. Shares 5 wt. % lumps having a minimum diameter of 1250 microns, and 37 wt. % of fine particles having a maximum diameter of 350 μm were separated.

Stage (e.4): The lumps obtained in stage (d.4) were crushed in a screening machine at 1435 rpm. Ground particles with a maximum diameter of 500 μm were collected and transferred to step (f).

Step (f.4) The crushed lumps obtained in step (e.4) were combined with the fine particles from step (c.4) and returned in portions to the granulator.

A free-flowing granule (A.1) was obtained which had excellent properties such as, but not limited to, excellent percarbonate stability and low hygroscopicity. No hot spots were observed during processing. No sticky material was obtained. A free-flowing granule was obtained and the hygroscopicity was low.

Example 5

Stage (a.5): the aqueous solution (A.1) was heated to 55 ° C.

A vessel containing a fluidized bed of 1 kg of solid MGDA-Na ₃ granules, an initial average particle diameter of 550 μm, was provided. Fluidization was carried out by introducing a so-called fluidizing gas at the bottom of the vessel, said fluidizing gas being air with an inlet temperature of 150 ° C.

Once a bed temperature of at least 93 ° C. was reached, an amount of 2 kg / h of the above aqueous solution (A.1) was sprayed onto the fluidized bed using a nozzle. Atomization - and so-called atomization - was carried out using air with an inlet gas temperature of 171 ° C and a pressure of 3.2 bar.

Step (b.5): Every 30 minutes, an aliquot of the pellet was removed from the vessel through the side discharge auger. The residual moisture content was 11.1 wt. %.

Steps (c.5) and (d.5): The aliquot recovered according to step (b.5) was classified by sieving in a twin sieve sieve, 350 µm and 1250 µm mesh. Shares 35 wt. % lumps having a minimum diameter of 1250 microns, and 4 wt. % of fine particles having a maximum diameter of 350 μm were separated.

Stage (e.5): The lumps obtained in stage (d.5) were crushed in a screening machine at 1435 rpm. Ground particles with a maximum diameter of 500 μm were collected and transferred to step (f).

Step (f.5) The crushed lumps obtained in step (e.5) were combined with the fine particles from step (c.5) and returned in portions to the granulator.

A free-flowing granule (A.1) was obtained which had excellent properties such as, but not limited to, excellent percarbonate stability and low hygroscopicity. No hot spots were observed during processing. No sticky material was obtained. A free-flowing granule was obtained and the hygroscopicity was low.

The results are shown in Table 2.

(D50) refers to a granule.

Claims (20)

1. A method of obtaining a powder or granule containing (A) at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA), where said alkali metal salts are selected from compounds according to the general formula (Ia)

where M is selected from alkali metal cations selected from sodium, potassium, or a combination of sodium and potassium, and x is in the range from zero to 1.0, wherein said method comprises the steps (a) introducing an aqueous solution or aqueous suspension of an appropriate chelating agent (A) into a spray granulator and removing most of said water by spray granulation using a gas with an inlet temperature of 125 to 250 ° C, (b) removing the granules from the spray granulator, (c) separating fine particles from said granules, wherein said fine particles have a maximum particle diameter of 350 μm, (d) separating lumps from said granules, wherein said lumps have a diameter of 1000 μm or more, (e) grinding said lumps to a maximum particle diameter of 500 μm in the case of granules, (f) reintroducing said fine particles from step (c) and crushed lumps from step (e) into the spray granulator, where the proportion of fine particles is in the range from 4 to 18 wt.% of the total chelating agent (A) recovered in step (b), and the proportion of crushed lumps from step (e) is in the range from 20 to 40 wt.% of the total chelating agent (A) recovered in step (b). 2. A process according to claim 1, wherein step (c) separates from 80 to 99% by weight of fine particles. 3. A method according to claim 1, wherein the aqueous solution or suspension in step (a) contains at least one (co) polymer (B), said (co) polymer (B) being selected from homo- and copolymers (meth) acrylic acid and polyalkyleneimines, which may be polyalkoxylated or substituted with carboxymethyl groups. 4. The method according to claim 3, wherein said granule contains in the range from 80 to 99.9% by weight of a chelating agent (A) and from 0.1 to 20% by weight of a (co) polymer (B), the percentages being refer to the solids content of said powder or said granule. 5. The method of claim 1, wherein the chelating agent (A) is MGDA trisodium salt. 6. A process according to claim 3, wherein said (co) polymer (B) is selected from sodium per-salts of polyacrylic acid. 7. A process according to claim 3, wherein said (co) polymer (B) is selected from polyethyleneimine, which may be polyethoxylated. 8. The method according to any one of claims. 3-7, wherein said (co) polymer (B) has an average molecular weight M _w in the range of 1200 to 30,000 g / mol, as determined by gel permeation chromatography and with reference to the corresponding free acid.